Method and apparatus for contacting gases and particle form solid material



May 11, l948 J. A. CROWLEY, JR., Er AL 2,441,311

METHOD AND APPARATUS FOR CONTACTING GASES AND PARTICLE FORM SOLID MATERIAL BY l M TTORNEY May 11, 1948. J. A. CROWLEY, JR., Er A1. 2,441,311

METHOD AND APPARATUS FOR CONTACTING GASES AND PARTICLE FORM SOLID MATERIAL Filed Oct. 14, 1944 3 Sheets-Sheet 2 4. Y M f, M /M /Mmr sas Y cof/marsa @as ourZ May ll, 1948. J. A. CROWLEY, JR., Er AL 2,441,311

METHOD AND APPARATUS FOR coNTAcTING GAsEs AND PARTICLE FORM soLID MATERIAL A Filed Oct. 14, 1944 3 Sheets-Sheet 3 ATTO R N EY Patented May 11, 1948 UNITED sTaTEs PATENT OFFICE METHOD AND APPARATUS FOR CONTACT- ING GASES AND PARTICLE FORM SOLID MATERIAL John A. Crowley, Jr., Scarsdale.' N. Y., and Charles V. Homberg, Wenonah, N. J., assignors to Socony-Vacuum Oil Company, Incorporated, a corporation of New York Application October 14, 1944, Serial No. 558,694

to contact with a particle form solid adsorbent material having catalytic properties at temperatures of the order of 800 F. to 950 F. and pressures usually above atmospheric. The solid adsorbent material may partake ofthe nature of natural clays and treated clays, such as fullers earth, Superfltrol and bauxite or of certain synthetic associations of alumina, silica or silica and alumina, any of which may contain added compounds such as certain metallic oxides. Recently this process has been developed as one wherein the particle form solid material is passed cyclically through two zones, in the iirst of which it is subjected to contact with hydrocarbon gases for the purpose of conversion and in the second l of which it is subjected to the action of a combustion supporting gas, such as air, acting to burn oir a contaminant material, deposited upon the solid material during the conversion step.

In such a cyclic process the solid material particles are subject to a. gradual attrition resulting in the gradual accumulation in the circulating mass of solid material of small amounts of undersized solid material particles. In order to obtain satisfactory operation in such cyclic processes, it is necessary to maintain the solid material particle size within certain ranges which are depend- I ent upon theparticular apparatus and process involved. It is consequently desirable to prevent undue accumulation of undersized solid particles in the circulating solid material mass. Usually a certain amount of undersized, and in some operations normal sized solid material particles will be entrained from the conversion and the solid material regeneration vessels in the eiiluent gas streams therefrom. In the case particularly 2 used for other external purposes. Consequently, it is desirable to return such entrained solid material to the conversion vessel, and remove the accumulating undersized material from some other part of the cyclic system, preferably 'directly following the regeneration step. It will, of course, be apparent that if the solid material entrained from the convertor be partly or entirely of normal size, its return to the convertor is per se desirable. This invention has specifically to do with method and apparatus for accomplishing the/ return of such entrained material to conversion vessels.

It has been found that the return of such solid materials entrained from conversion vessels is complicated by two factors. First, if the entrained solid material is undersized and corresponding to a powder in formit will tend to bridge and clog the drain conduit from the gassolid separator. Second, in some operations the contaminant deposit may besticky also causing the solid material to clog drain conduits especially if such conduits are relatively small in size. Such bridging or clogging of the separator drain conduits not only prevents the return of such material to the conversion vessel but may also result in the accumulation of` solid material in the separator making its proper operation lrnpossible. Another diiliculty arises in that when a concentrated stream or mass of principally undersized solid material particles is returned to the conversion vessel, the eilluent gas on contacting said concentrated mass of undersized material will tend to again entrain substantially all of it from the convertor.

A major object` of this invention is the provision in a process wherein a gas is contacted with a moving particle form solid material, of a method and apparatus for return to the contacting vessel of solid material particles entrained from said contacting vessel in the eilluent gas stream.

Another object of this invention is the provision in such a cyclic conversion system as hereinof the conversion vessel this is undesirable, be-

cause the solid material entrained therefrom will be entrained in the hydrocarbon gas stream and,

. consequently, said solid material will contain certain contaminant deposits. If this material is l separated from the eilluent gas and removed from the system, a subsequent diilicult regeneration of the undersized material will be required before the undersized material may be reprocessed or above described of `a method for returning entrained undersized contact massA material to a conversion vessel by gravity ow and in such a way as to substantially limit the immediate reentrainment thereof inthe eiiluent gas stream from said conversion vessel.

These and other objects of the invention will appear in the following description of the drawings attached hereto oi which Figure 1 is an.

l elevational flow diagram of a cyclic conversion Y process and Figure 2 is an elevational view, partially in section showing the upper end of a con- Yelslim Vessel and the application of the appa- 3 ratus of this invention. Figure 3 is a similar view showing a modined form of the-invention. All

of these drawings are highly diagrammatic in invention. The term undersized particle form,-

solid material is intended to mean solid material of a particle size or of a range of particle sizes. the average of which is substantially less than the average particle size of the main stream ofy solid material cyclicallypassed through the particular system involved. 'I'he term gas or gaseous rel actants. etc., is 'intended to cover material which is substantially in the gaseous phase at the operation conditions involved, regardless t o1.'v what may be the normal phase of such material at atmospheric conditions.

g now to Figure 1, we-nd a conversion vessel III having a reactant gas inlet II, and gaseous product outlet I2, a solid material outlet conduit I3 having la. throttle valve I4 thereon. 'I'he outlet conduit I3 connects into a suitable conveyor I5 by which the spent solid material withdrawn from the convertor is conveyed upwardy to be discharged into conduit I3 feeding the regenerator vessel -I 1. The regenerator shown is of multistage type having several inlets I3 to which combustion supporting gas is introduced from the main inlet duct I Sand riser'duct 2'0. Spent regeneration gas outlet ducts 2| are provided which connect into riser ducts 22. The spent regeneration gas passes from ducts 22 into and upwardly through an elutriator 23 wherein a relatively small stream of regenerated solid material introduced through conduit f 24 is countercurrently scrubbed by at least part oi' the enluent regeneration gas for removal of undersized solid particles from the system. The undersized material is entrained in the eiiluent'gas stream through outlet conduit 25 into a cyclone separator 26 wherein the gas-solid separation is accomplished, the separated undersized solid material being withdrawn through pipe 2l and the gas through pipe 28. Scrubbed normal size solid material particles pass Yfrom the elutriator through pipe 29 into the regenerator. The regenerator is provided with a drain conduit 30, having throttle valve 3i thereon through which regenerated solid material passes to the conveyor 32. It is then conveyed upwardly and discharged through conduit-33 into an accumulation hopper 34. A chamber 35 is positioned between the hopper 34 and convertor I0, and this chamber is provided with a conduit 3B havingk an instrument operated valve 31 thereon for admittance of an inert seal gas into the chamber 35. A substantially vertical conduit 38 extends between the hopper 34 and chamber 35. the conduit 38 being of suilicient vertical length to permit maintenance of a suilicient head of particle form solid material therein to permit gravity dow of the solid material into the chamber 35 against the gaseous pressure therein. A substantially vertical conduit 43 extends between the seal chamber 35 and the top of the convertor III. AA

valve 4S is provided in conduit to permit control of the flow of solid material in the conduit to the convertor. A conduit 42 is connected between the conduit 43 and the upper section of a conduit 4I 70 which in turn is connected between a cyclone separator 39 and the top of the convertor. A valve 45 is provided in conduit 42 to permit control of solid flow therethrough. The cyclone separator may be or any of a number of conventional types 45 The gaseous reaction section 41 and drain conduit 4I tween said section and the top oi' the convertor .v substantially illled with solid material up to thel level of the connection of conduit 42 into said In operation solid material is cyclically passed downwardly through the convertor I0 and the regenerator Il. the flow from each of said vessels being throttled by means of throttle valves I4 and I\ 3l. respectively, so as to maintain substantially A 'compact columns of said solid material in said vessels. A small side stream of regenerated solid material is passed through the elutriator 23 as hereinbefore described for the purpose of limit- 10' ing the accumulation of excess quantities of'undersized solid material in the cyclically owing solid material stream.' The range of solid material particle size in said cyclically flowing stream is to some extent dependent upon the type of con- 15 version system involved. Thus for a system, such as shown, wherein the solid material ilows through the vessel as substantially solid columns through which gases flow, a particle size range of 8 to 30 mesh has been found entirely satisfacgg tory. In operations wherein relatively low gas throughput rates are involved, a particle size range of 66 to 100 mesh has been found acceptable. The undersized material which should be removed in the rlrst example would be material g5 substantially smaller than 30 mesh and especially material smaller than say mesh.

Continuing a study ofthe operation of the system shown in Figure l, reference should now also be made to Figure 2 wherein the upper end of the 3 convertory ls shown along with. a somewhat modilied form of the auxiliary solid material feed and gas withdrawal apparatus and wherein like numerals are used for like members. Reactant gases, such as vaporized hydrocarbons preheated 35 to a suitable conversion temperature in a suitable external apparatus (not shown) pass into the convertor through conduit II. The gas then passes through the column of solid material in the convertor, disengages therefrom in the zone 50 pro- 40 vided between pipes 5I in the upper end thereof and passes through outlet conduit I2 into a cyclone separator 39. In the separator substantially all or part of the solid material entrained from the convertor is separated from'the gas. products are withdrawn through pipe 40 to a suitable product recovery system, not shown. and the separated solid material drops into the enlarged section 41 connected to the conical shaped bottom of the separator.

5o This enlarged section may alternatively take the form of a separate chamber below the separator 39 and connected thereto by a suitable conduit or conduits. Such a chamber is shown at 41' in Figure 3, the remaining elements in Figure 3 55 being the same as in Figure 2. Buch enlarged chambers permit better settling of the separated solid material from the separator 39 especially when the gaseous pressure in the separator is less than that in chambers 35 or 52. The enlarged o section also permits better mixing of the separated and the normal sized feed solid material. A stream of normal sized feed material for the convertor passes into the enlarged section 41 through the conduit 42, thereby maintaining the material flowing into conduit 4I, mixes with the normal sized solid material and passes therewith through conduit 4I into the head chamber 52 of connected bein respectively.

-the convertor onto the bed of solid material 53 conduit 42, the remainder may be passed from seal chamber to the convertor by way of conduit 43, the relative fiow in conduits 42 and 43 the solid column flow throughthe conversionl vessel due to gas flow therethrough and the tendency for the gas to re-entrain the undersized material is substantially reduced.

Whereas 'the apparatus of this invention has been found particularly useful in a process of the type described, it is not limited thereto.' Such a method and apparatus for returning solid parbeing adjusted by means oi valves 45 and 46 there- Since the 4flow of solid"materiai from the convertor is so throttled as to maintain the convertor substantially lled withsolid ma- 'I terial, the iiow of solid material from conduit 4t 4 will be throttled by the bed of solid material 53 in theconvertor head section 52. Consequently,

the conduit 4I- will always be substantially illled' strument operated flow control valve 31 so thatA the gaseous pressure in chamber 35 is at least equal and preferably slightly greater, say 1/4 to V; pounds per square inch than the gaseous pressure 'in the separator 39 or in the head section 52 of the convertor. Thus, the escape into the atmosphere of combustible reactant gases is prevented. As has been shown hereinbefore regenerated particle form solid material is introduced into the seal chamber 35 from the surge hopper 34 by way of the gravity flow leg 38. If desired, other means may be used for introducing the solid material into chamber 35 against the gaseous pressure therein; such means may, for example, comprise star wheels, screw conveyors or systems of automatically operated lock chambers.

It the escape of a small amount of reactant gas is not objectionable. thenl in such operations, the seal chamber 35 may be omitted and solid material `feed may be all, or in part. conducted directly from the surge feed hopper 34 or from gravity feed conduit 38 into the enlarged section 41 below the separator. In less preferable arrangements enlarged section 41 may also be omitted and the normal sized solid material injected from conduit 42 into the lower end of the conical drain section of the separator 39. The

sired, by other suitable confined apparatus for solid-gas separation, but the use of the cyclone separator has been found preferable for such operations as hereinabove described.

By the method and apparatus hereinabove described, `a stream of regenerated particle form solid material, free from cokey contaminant deposits and of an average particle size suitable for the operation involved is mixed with a stream of undersized contaminant bearing solid material particles which have been separated from an entraining gas stream, and the combined streams are passed through a conduit by gravity ow into a contacting or conversion vessel. The addition of the larger and contaminant free'solid material particles to the stream of undersized contaminant bearing particles, eiectively eliminates tlcles to a contacting or conversion vessel may also be used'vwhen the solid material flow within such vessels isA not as a substantially' compact column but as a rain of vsolid material or as solid material entirely or partially carried in a gas stream. When theapparatus is applied to such operations, the internal cross-section of the conduit 42 should be substantially greater than that of conduit 4i so as to avoid the possibility of the loss of a seal leg of solid material in the conduit 4l.

The drawings hereto attached, the description thereof and the description of the application of this inventionhave been intended as exemplary and are not to be'construed as limiting this invention except as it may be limited in the fol'- `lowing claims.

We claim:

1. Ina system for contacting gases with movlng particle form solid material, a vessel adapted for contacting gases and solids therein and for passage of gases and particle form solids therethrough, means adapted for substantial separation oi the entrained solid material particles lfrom the eilluent gas stream from said vessel. conduit means extending downwardly from said separa- -tion means to a location within said vessel, for

return oi' said separated solid material to said contacting vessel, a chamber adapted to confine a` bed of particle-form solid contact material under a gaseous pressure positioned above said separator, means to introduce particle form solid contact mass material feed for said contacting vessel into said chamber, means to maintain a suitable seal gas pressure in said chamber above the gaseous pressure in said separation means, means to deliver at least a part of the solid material feed from said chamber into said conduit extending from said separation means to said contacting vessel at a location adjacent its connection to said separation means. v

2. In a system for conducting gaseous conversions in the presence of a particle form solid contact mass material, avessel adapted for contact of a moving stream of gas with a moving stream of particle form contact mass material therein, a solid gas separation apparatus positioned above said vessel for separation of entrained undersized solid particles from the efiiuent gas from said vessel and means for directing said eiiluent gas through said separation apparatus, conduit means extending from said separation apparatus to a location within said vessel for return by gravity flow of separated solid material particles to said vessel, a solid feed supply chamber positioned above said separation apparatus, passage defining means extending between said chamber and a point adjacent the connection of said rst named conduit with said separation apparatus for now of a portion of the solid feed material in to said rst named conduit, said pas'-v therethrough of a stream of gaseous reactants in contact with a movingstream oi particle form solid contact mass material passing therethrough, a gas solid separatlonapparatus positioned abovesaid vessel and means for directing eiliuent gas carrying entrained undersized contact mass material from said vessel through said separation apparatus. conduit means extending from said separation apparatus to said vessel for return by gravity ilow oi separated solid material to said vessel, means deiining a chamber adapted to conilne a bedioi particle form solid contact mass material under a gaseous pressure, said chamber being positioned above said separation apparatus, means to introduce particle form solid contact mass material feed for said vessel to said chamber, passage defining means extending between said chamber and a. point on said conduit adjacent its connection to said separation vessel for ilow of at least part of said solid material feed into said conduit, said passage defining means being of greater internal cross-section'than said conduit,'means to maintain an inert gas pressure in said chamber above the gaseous pressure in said 'separation apparatus.

4. In a processwherein a particle form solidy material is introduced into and passed through a confined contacting zone and wherein a contact gas is Passed through said zone in ,contact with said solid material, then substantially disengaged therefrom andl passed througha suitable separator for removal of entrained solid material particles, an improved method for returning said separated solid'material to said contacting `zone comprising introducing at leastI part ofthe solid material feed stream for said contacting zone into the stream of separated solid material passing from said separator close to the point where said stream of separated solid` material passes from said separator 'and passing the mixed solid material as a conilned compact stream to said contactingy zone and maintaining the rate of introduction of said solid feed stream at said point where said stream of separated solid passes from said separator suiliciently high at all times to insure continuity of compactness all along the length of said mixed stream up tol said point where the separated solid passes from said separator. A Y

5. In a gaseous conversion system comprising a conversion vessel adapted for passage therethrough of a stream o! gaseous reactants in contact with a stream of particle form solid contact mass material passing therethrough and a gassolid separator for removal oi entrained underlsized particle form solid material from the effluent gas stream from said conversion vessel, the improved method for returning said separated undersized solid material to said conversion vessel consisting of maintaining a compact gravitating stream of mixed separated solid 'material and normal sized particle form solid material in a confined passage between said conversion vessel and a location close below said separator, causing said separated solid material to drop from said separator substantially directly Vonto the upper end oi said stream of mixed solids at said location close below said separator, directing a gravitating confined, compact stream of normal sized particles into the upper end of said stream of mixed solids at a rate sumcient to continuously maintain said conilned passage full `and said stream of mixed solids compact up tov said location close below said separator.

6. A method for conducting gaseous couver-l slons'in the presence of a moving particle i'orm solid contact mass material comprising passing gaseous reactants through a confined conversion zone in contact with a particle form solid contact mass ,material passing through said zone. withdrawing gaseous conversion products from said conversion zone. substantially separating any ventrained solid material from said eilluent gas stream from said conversion'zone'in' a suitable separation zone, maintaining a compact stream Aoi' mixed separated solid material andcoarser solid material betweensaid conversion zone and e pointclose below said separationzone thereabove, flowing mixed solids from the lower end of said stream into seid conversion zone, causing the solid material separated in vsaid separation zone to drain immediately into the upper end vof said stream of mixed solids to partially' replenish said stream oi*y mixed solids, and directu ing a stream of the coarser feed solids which is larger than saidstream of mixed solids onto the: upper end of said stream of mixed solids to com-v' pletely replenish said stream of mixed solids and to maintain the level of its upper end constant and close below said separation zone.

7; A method for conducting gaseousy conversions in the presence of a particle form solid contact mass material consisting of the steps: passa able solid-gas separator, .withdrawing the substamtiallyv solid-free gaseous products from said separator, returning the separated particle form solid material to said conversion zone in a conned gravity flowing stream; and at the same time maintaining at a location above said separator a conned bed of normal sized particle form solid contact mass material under an inert gaseous pressure somewhat greater than the gaseous pressure in said separator, continuously passing solid material from said conilned bed as a substantially compact coniined stream into said stream of returning undersized solid material so that the mixed solid material may pass together to said conversion zone as a substantially compact gravity flowing stream, and continuously replenishing said conned bed of solid material.

8. In a gas solid contact process a method for introducing two types-of particle form solid material streams to a conned contacting zone, one

stream consisting principally of particles of small average particle size and the' other stream consisting principally of particles of relatively larger average particle size, which method comprises, introducing all oi' the stream oi' solid material of small average particle size and at least part of the stream of solid material of large average particle size into an enlarged chamber maintained above said contacting zone, passing the mixed solid material as a confined compact gravity ilowing stream to said contacting zone, maintaining the rate of supply of the contact material of large particle size suillciently high to provide a bed ofk contact material of substantially constant surface level in said enlarged chamber and passing any remaining portion of said stream o! solid material of large average particle size as 9 a separate, confined compact stream to said contacting zone.

9. In process for gaseous conversion in the presence of particle form solid materials of large and small particle size a, method for continuously` introducing the large and small particle size solid materials to the connned conversion zone which method comprises: mixing allof the solid feed material of small particle size with'part of the solid feed material of large size in a confined chamber above said contacting zone, passing the mixed solid material as a substantially compact confined gravity flowing stream to said conversion zone, limiting the rate of supply of the large size feed material to said confined chamber only to that required to maintain a compact bed in said confined chamber and passing the remaining portion of the solid feed material of large size as a separate, substantially compact conined gravity flowing stream to said conversion zone. 1

gravitiy flowingi along withany entrained undersized solid material through a suitable solid-gas separation zone,

withdrawing substantially solid-free gaseous material from said. separation` zone, returning the separated particle form solid material to said contacting zone in a confined gravity flowing 10. In a system for contacting gases with movan enlarged chamber directly below and close to said separator, conduit means for passage oi eiiiuent gas and entrained solid material: from said vessel to said separator, conduit means for supplyv of normal sized solid materialfeed particles into said enlarged chamber, conduit means of smaller cross-'sectional area than said en- "larged chamber connected between said enlarged chamber and said vessel for downward ow of mixed separated and feed solidparticles to said vessel.

11. In a processwherein 9, particle form solid Y smaller cross-sectional size than said compactv stream of solid feed material, permitting said compact stream of solid feed material to freely iiow onto said compact stream of mixed solid1 material so as to maintain the latter continuously compact up to the level of the stream mixing, and replenishing said confined bed with normal sized feed solidmaterial.

13. In a process wherein a fluid material is subjected to contact =in a confined contacting zone with moving particle form solid material which is supplied to said zone as solid feed particles averaging substantially greater than 100 mesh Tyler screen in size and wherein contacted gaseous material is withdrawn from said zone carrying some entrained solid material averaging less than about 100 mesh Tyler screen in size, the improved method for returning said entrained solid material to said contacting zone comprising: passing said gaseous material and entrained solids from said contacting zone through a suitable solid-gas separation zone to eilect separation of the entrainedI solids from said gaseous material, introducing at least part of the solid material is introduced into and passed through a connned contacting zone and wherein a contact gas is passed through said zone in contactwith said solid material, then substantially disengaged therefrom and passed through a suitable gassolid separation zone for removal 'of entrained undersized solid material particles, an improved method for returning said separated undersized solidmaterial to said contacting zone which comprises causing said separated undersized-solid material ,to drop directly from said separation zone onto abed of solid material in a vconterminous drain zone having a substantialcross-sectional area, introducing at least a portion of the feed stream of normal ,sized solid material partirated undersized solid material, limiting the rate of normal sized solid introduction onto said drain zone only to that required to maintainthe surface levelof said bed substantially constant and passing the mixed soiid material as a substancontacting zone.

12. A method for contacting fluids with partially compact gravityfiifowing stream to said ticle form solid materials comprising the steps passing particle form solid material through a confined' contacting zone .while contacting said particle feed stream for said contacting zone into the stream of separated, smaller sized solid particles passing from said separation zone at a location close to that where said stream of separated solid material passes from said separation zone, passing the mixed solid material as a substantially compact, gravitating stream to said contacting zone, and limiting the -rate of introduction of said feed stream into said stream of sepa- 'cles into said drain zone to mix with saidsepay' 1,448,778 Witte 1 Feb. 27, 1923 2,298,722 Marancik et al. Sept. 22, 1942 2,302,209 Goddin Nov. 17, 1942 2,302,328l Kel1y1 Nov. 17, 1942 2,325,611 Keranen -..L Aug. 3, 1943 i 2,356,717 Williams Aug. 22, 1944 2,360,787 Murphree t al. ....--.Och 17, 1944 2,369,523 Belchets -..^Feb, 13, 1945 2,379,448 Linn .July 3, 1945, 2,384,355 Tyson Sept. 4, 1945 2.391.334 v Nicholson Dec. 18, 1945 rated smaller sized particles only to that required to continuously maintain said stream of mixed solid material compact up to; the level of the feed stream introduction as aforesaid.

JOHN A. CROWLEY, Jn, CHARLES V. HORNBERG.

REFERENCES `CITED The following references are of record in the4 meoftliis patent:

- UNITED STATES PATENTS Number i -Bi'inpson' et al. Oct. 15,1948 

